Treatment of textiles with glycidol-modified polyurethanes

ABSTRACT

POLYURETHANES CONTAINING ISOCYANATE GROUPS ARE REACTED WITH GLYCIDOL TO PREPARE GLYCIDOL-MODIFIED POLYURETHANES USEFUL FOR APPLICATION TO TEXTILE MATERIALS TO IMPROVE THEIR PROPERTIES, E.G., TO IMPART SHRINK RESISTANCE. TYPICAL EXAMPLE: A POLYETHER POLYURETHANE CONTAINING FREE NCO GROUPS IS REACTED WITH GLYCIDOL TO YIELD A GLYCIDOL-MODIFIED POLYMER WHICH IS FORMED INTO AN EMULSION AND APPLIED TO A TEXTILE MATERIAL. THE TREATED TEXTILE MAY BE DIRECTLY CURED OR THE CURING OPERATION MAY BE DELAYED UNTIL THE FABRIC IS MANUFACTURED INTO A FINISHED GARMENT.

United States Patent 3,814,578 TREATMENT OF TEXTILES WITH GLYCIDOL-MODIFIED POLYURETHANES Allen G. Pittman, El Cerrito, and William L.Wasley and Carlton C. Jones, Berkeley, Calif., assignors to the UnitedStates of America as represented by the Secretary of Agriculture NoDrawing. Filed Jan. 14, 1972, Ser. No. 217,963 Int. Cl. D06m 3/08, 15/52U.S. Cl. 8127.6 7 Claims ABSTRACT OF THE DISCLOSURE Polyurethanescontaining isocyanate groups are reacted with glycidol to prepareglycidol-modified polyurethanes useful for application to textilematerials to improve their properties, e.g., to impart shrinkresistance. Typical example: A polyether polyurethane containing freeNCO groups is reacted with glycidol to yield a glycidol-modified polymerwhich is formed into an emulsion and applied to a textile material. Thetreated textile may be directly cured or the curing operation may bedelayed until the fabric is manufactured into a finished garment.

A non-exclusive, irrevocable, royalty-free license in the inventionherein described, throughout the world for all purposes of the UnitedStates Government, with the power to grant sublicenses for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

DESCRIPTION OF THE INVENTION This invention relates to and has among itsobjects the provision of novel processes for treating textile materialsand the products of such processes. A special object of the invention isthe provision of such treatments involving the use of glycidol-modifiedpolyurethanes whereby to provide such benefits as improved shrinkageresistance and permanent press qualities. Further objects and advantagesof the invention will be evident from the following description whereinparts and percentages are by weight unless otherwise specified.

It is well-known in the art that many textile fibers exhibit poordimensional stability. For example, laundering causes severe shrinkageof woolen textiles. This technical disadvantage seriously restricts theapplications of Wool in the textile industry and much research has beenundertaken in order to modify the natural fibers in order to providethem with resistance to shrinking. Among the procedures advocated forthis purpose are those wherein a polyepoxide and a compound containing aplurality of amino groups, typically a polyamine or apolyamine-polyamide, are co'applied to the textile. See U.S. Pats.2,869,- 971 and 3,019,076.

We have found that a novel class of glycidol derivatives exhibits anunusual ability to improve the properties of textiles, particularlywool. Our agents are not only chemically distinct from those of theprior art, but also obviate problems inherent in the prior arttechniques. Some of the significant advantages provided by our glycidolderivatives are listed below:

They provide effective shrinkproofing even when applied in smallproportion to the textile material.

They are effective per se: Conjoint application of a polyamine orpolyamino-polyamide is unnecessary. It may ice be noted in thisconnection that application of polyamines or polyamino-polyamides towool is hazardous because these reagents tend to cause yellowing of thetreated fibers. The compounds of the invention have the advantage thatthey do not cause yellowing of wool or other textile fibers. They do notadversely affect the resistance of the treated textiles to soils, andthey do not adversely affect the ability to remove soil by conventionalwashing procedures. In contrast, textiles treated with the known epoxidecompositions tend to become soiled more readily than the untreatedtextile, and on washing are subject to soil re-deposition problems.

They are useful in applications involving delayed curing, that is, wherethe glycidol derivative is applied to the fabric, and the treated fabriccured only after a considerable delay, for example, after the treatedfabric has been manufactured into a garment. This permits the compoundsof the invention to be used in conjunction with agents which providepermanent press qualities to the textile. The particular advantage ofthe present invention which makes it especially adapted to such use isthat our glycidol derivatives do not undergo spontaneous curing; theyremain in the uncured state even after long storage of the treatedfabric. In contrast, prior art treatments with epoxides and polyaminesor polyamino-polya-mides cannot be used in delayed curing systemsbecause they undergo spontaneous curing when held at room temperatureeven a few days.

Dispersions of the compounds of the invention exhibit a long pot-life sothat a single batch of the dispersion may be prepared for treating largeamounts of textile material. In contrast, prior art formulations ofepoxides and polyamines or polyamino-polyamides have a short pot-life inthat they tend to gel and become useless in a short time.

They do not affect the intrinsic properties of the fibers such as color,tensile strengh, abrasion resistance, flexibility, hand, porosity, etc.so that the treated fibrous materials can be employed in any of theusual textile applications as in fabricating shirts, skirts, trousers,and other garments, blankets, draperies, carpets, etc.

The compounds of the invention may aptly be termed as glycidol-modifiedpolyurethanes, and have the structure:

(Formula I) wherein:

n is an integer from 2 to 4, and x is an integer from 1 to 2.

The glycidol derivatives of the invention are prepared by reactingglycidol, in the presence of a suitable catalyst, with a polyether (orpolyester) polyurethane containing free isocyanate groups. This simplereaction establishes the desired glycidol-modification of the startingpolymer.

3 4 A typical, but by no means limiting, example of the synof freeisocyanate groups in the product. A typical, but thesis is illustratedbelow: by no means limiting, example 18 illustrated below:

Y HO CH;CH CH -CH;O H Polyether polyol OCN NHil*- -omcmcm CH; o 9

| 10 2 N00 Polyisocyanate o Isocyanate-terminated Hl-IJH N00 polyetherpolyurethane l .-i-. CH:

0 HO OH Ch \CH Glycldol 0 i a 0 CN NH 0 -GH;CH;CH CH;O l

CH: OH;

l o O O O 1 U a, NH NCO om-cn-cm-o- -NH NH- 0-oH=cH,-

Isocyanate-terminated (12Ha polyether polyurethane 0 0 (In the aboveformulas, m represents the number of 1- a a tetramethylene-etherrepeating units. This may range, for

example, about from 5 to 50.).

Representative examples of polyisocyanates which may mymdmmdmed beemployed for reaction with the polyether (or poly- Pmyethe Pdyurethaester) polyol include:

(In the above formulas, m represents the number of tetrat1uene-2,4-diis0cyanate methylene-ether repeating units. This may range,for ex- 1 .2,6-dii t ample, about from 5 to 50.) commercial mixtures oftoluene-2,4 and 2,6-diisocyanates The raction of the polyurethane andglycidol is carried ethylene diisocyanate out at about 50-70 C., andunder essentially anhydrous 4O ethylidene dii conditions to avoidhydrolysis of the isocyanate groups. l .1,2 dii te The glycidol issupplied in the amount necessary to obtain l h l -1 2.dii t conversionof all the isocyanate groups to glycidyl groups.cyclohexylene-l-4-diisocyanate The reaction is promoted by the presenceof catalysts such h 1 diisgcyanate as dibutyltin dilaurate or an aminesuch as piperidine or 3,3'-di h l-4,4'-bi hen 1 ne diisocyanatecombinations of these. 4,4-biphenylene diisocyanate Referring to FormulaI, above, it is evident that selec- 3,3'-dichloro-4,4'-biphenylenediisocyanate tion of the polymer intermediate-the polyether or poly-1,6-h h l dii o t ester polyurethane containing free isocyanate groups-1,4-tet1-amethylene-diisocyanate Will determine the values Of A, R, R',n, and x. The 1,10-decamethylenediisocyanate preparation of theseintermediates is well-known in the 1,s-naphthalenediisocyanate art; theyare widely used in the production of urethane cumene-ZA-diigogyanatefoams for padding and insulation applications, and in the4-methoxy-1,3-phenylenediisocyanate production of elastomers. Althoughthe preparation of 4-chloro-1,3-phenylenediisocyanate theseintermediates forms no part of the present invention,4-bromo-1,3-phenylendediisocyanate this subject will be explained belowto illustrate the wide 4-ethoxy-l,3-phenylenediisocyanate range ofinermediates which may be empolyed in produc-2,4'-diisocyanatodiphenylether ing the glycidol derivatives of theinvention. Thus, for 5,6-dimethyl-1,S-phenylenediisocyanate the purposesof the invention, the intermediate may be2,4-dimethyl-1,3-phenylenediisocyanate any polyether or polyesterpolyurethane which contains 4,4-diisocyanatodiphenylether at least twofree NCO groups per polymer molecule. Pre- 0 benzidinediisocyanateferred are the polymer intermediates having a molecular ,6- im hy-1,3-phenylenediisocyanate weight of at least 500, more preferably thosehaving a 9,1o-a y molecular weight of at least 1000. Also, it isgenerally 4,4'-diiS0CyaHat0dibnZY1 preferred to use the polyether-basedpolymers, for ex- 3,3-dimethyl-4,4'-diisocyanatodiphenylmethane ample,the NCO-containing polyurethanes derived from 2,imethy1-4,4'-diisoeyanatodiphenyl polyalkylene ether glycols such aspolyethylene ether gly- ,4'- y nat0dibenzyl cols, polytrimethylene etherglycols, polytetramethylene 2, y n ilb ne ether glycols,polypropyleneether glycols, and the like. a;g $Y Y p y imeoxy-4,4'-diisocyanatodiphenyl THE POLYMER INTERMEDIATES1,4-anthracenediisocyanate Polyether (or polyester) polyurethanescontaining free 2,5-fluorenediisocyanate isocyanate groups useful asintermediates for the present 1,8-naphthalenediisocyanate invention maybe prepared, as well-known in the art, by 2,6-diisocyanatobenzfuranreacting a, polyether (or polyester) polyol with a polyiso-2,4,6-to1uenetriisocyanate, and cyanate, using an excess of the latterto ensure provision p,p',p"-triphenylmethane triisocyanate.

It is evident that the selection of the polyisocyanate reactant willdetermine the values of R and R in Formula I. For example, where thereactant is a hydrocarbon diisocyanate, R will be a hydrocarbon radicaland R will represent a hydrogen atom forming part of said hydrocarbonradical. Where the reactant contains a substituent such as chlorine ormethoxy-as would be the case with, for example, 4 chloro-1,3-phenylenediisocyanate or 4-methoxy-1,3-phenylene diisocyanateR will be thehydrocarbon residue of the reactant and R' will be thesubstituentchlorine or methoxy in the given examples.

The polymer intermediates useful for the purposes of the invention may,in turn, be derived from any of a wide variety of polyether polyols andpolyester polyols, and representative examples of these polyols aredescribed below:

Among the polyether polyols which may be so used are those prepared byreaction of an alkylene oxide with an initiator containing activehydrogen groups, a typical example of the initiator being a polyhydricalcohol such as ethylene glycol. The reaction is usually carried out inthe presence of either an acidic or basic catalyst. Examples of alkyleneoxides which may be employed in the synthesis include ethylene oxide,propylene oxide, any of the isomeric butylene oxides, and mixtures oftwo or more different alkylene oxides such as mixtures of ethylene andpropylene oxides. The resulting polymers contain a polyether backboneand are terminated by hydroxyl groups. The number of hydroxyl groups perpolymer molecule is determined by the functionality of the activehydrogen initiator. For example, a difunctional alcohol such as ethyleneglycol (as the active hydrogen initiator) leads to polyether chains inwhich there are two hydroxyl groups per polymer molecule. Whenpolymerization of the oxide is carried out in the presence of glycerol,a trifunctional alcohol, the resulting polyether molecules contain anaverage of three hydroxyl groups per molecule. Even higherfunctionalitymore hydroxyl groups-is obtained when the oxide ispolymerized in the presence of such polyols as pentaerythritol,sorbitol, dipentaerythritol, and the like. In addition to those listedabove, other examples of polyhydric alcohols which may be reacted withalkylene oxides to produce useful polyether polyols include:

propylene glycol trimethylene glycol 1,2-butylene glycol 1,3-butanediol1,4-butanediol 1,5-pentanediol 1,2-hexylene glycol 1,10-decanediol1,2-cyclohexanediol 2-butene-1,4-diol 3-cyclohexene-1,1-dimethanol4-methyl-3-cyclohexene- 1, l-dimethanol 3-methylene-1,5-pentanedioldiethylene glycol (2-hydroxyethoxy)-l-propanol4-(2-hydroxyethoxy)-l-butanol 5-(2-hydroxypropoxy)-l-pentanol1-(2-hydroxymethoxy)-2-hexanol 1-(2-hydroxypropoxy)-2-octanol3-allyloxy-1,5-pentanediol 2-allyloxymethyl-Z-methyl-1,3-propanediol(4-pentyloxy)methyl]-1,3-propanediol3-(o-propenylphenoxy)-l,2-propanediol thiodiglycol 2,2- [thiobisethyleneoxy) diethanol polyethyleneether glycol (molecular weight about200) 2,2'-isopropylidenebis (p-phenyleneoxy)diethanol 1,2,6-hexanetriol1,1,1-trimethylolpropane 3-(2-hydroxyethoxy)-1,2-propanediol3-(2-hydroxypropoxy)-1,2-propanediol2,4-dimethyl-2-(2-hydroxyethoxy)methylpentanediol-l,5

1,1,1-tris[ (2-hydroxyethoxy)methyl] ethane 1,1,1-tris[(Z-hydroxypropoxy methyl] propane triethanolamine triisopropanolamineresorcinol pyrogallol phloroglucinol hydroquinone 4,6-di-tertiarybutylcatechol catechol orcinol methylpholorglucinol hexylresorcinol3-hydroxy-2-naphthol 2-hydroxy-l-naphthol 2,5-dihydroxy-1-naphtholbis-phenols such as 2,2-bis (p-hydroxyphenyl) propane andbis-(p-hydroxyphenyl)methane 1,1,2-tris-(hydroxyphenyl)ethane1,1,3-tris-(hydroxyphenyl) propane.

An especially useful category of polyether polyols are thepolytetramethylene glycols. They are prepared by the ring-openingpolymerization of tetrahydrofuran, and contain the repeating unit in thepolymer backbone. Termination of the polymer chains is by hydroxylgroups.

The polyester polyols which may be employed as precursors for thecompounds of the invention are most readily prepared by condensationpolymerization of a polyol with a polybasic acid. The polyol and acidreactants are used in such proportion that essentially all the acidgroups are esterified and the resulting chain of ester units isterminated by hydroxyl groups. Representative examples of polybasicacids for producing these polymers are oxalic acid, malonic acid,succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic acid,fumaric acid, glutaconic acid, a-hydromuconic acid, fl-hydromuconicacid, a-butyl-a-ethylglutaric acid, a,p-diethylsuccinic acid, o-phthalicacid, isophthalic acid, terephthalic acid, hemimellitic acid,trimellitic acid, trimesic acid, mellophanic acid, prehnitic acid,pyromellitic acid, citrc acid, benzenepentacarboxylic acid, 1,4cyclohexanedicarboxylic acid, diglycollic acid, thiodiglycollic acid,dimerized oleic acid, dimerized linoleic acid, and the like.Representative examples of polyols for forming these polymers includesethylene glycol, 1,3-propylene glycol 1,2-propylene glycol, 1,4butyleneglycol, 1,3-butylene glycol, 1,2-butylene glycol, butene-1,4-diol,1,5-pentane diol, 1,4-pentane diol, 1,3-pentane diol, 1,6-hexane diol,hexene-l,6-diol, 1,7-heptane diol, diethylene glycol, glycerine,trimethylol propane, 1,3,6-hexanetriol, triethanolamine,pentaerythritol, sorbitol, and any of the other polyols listedhereinabove in connection with the preparation of polyether polyols.

An interesting class of polyester polyols are those which includepolyether units so that they may be considered as polyester polyols oras polyether polyols, depending on whether the ester or the ether groupsare in majority. The compounds may be produced by the condensationpolymerization of any of the above-mentioned polybasic carboxylic acidswith a polyalkyleneether glycol-typically, a polyethyleneether glycolhaving a molecular weight of about 200 to 2000using the glycol in therequired proportion to assure termination by hydroxyl.

Esters of the hydroxyl-containing acid, ricinoleic acid, form anothercategory of useful polyester polyols. Typically, one can use esters ofricinoleic acid with ethylene glycol, propylene glycol, glycerol,pentaerythritol, diglycerol, dipentaerythritol, polyalkyleneetherglycols, and the like. Representative of this category of polyesterpolyols 7 is castor oil which is composed mainly of the tri-glyceride ofricinoleic acid.

APPLICATION OF THE GLYCIDOL DERIVATIVES TO THE TEXTILE The compounds ofthe invention may 'be applied to the textile in various ways. Onetechnique involves dissolving the compound in an inert, volatile solventand applying the resulting solution to the textile material. Typical ofthe solvents which may be used are benzene, toluene, xylene, dioxane,diisopropyl ether, dibutyl ether, butyl acetate, chlorinatedhydrocarbons such as chloro form, carbon tetrachloride, ethylenedichloride, trichloroethylene, 1,3-dichlorobenzene, fluorohydrocarbonssuch as benzotrifluoride, 1,3-bis-(trifluoromethyl)benzene, etc.,petroluem distillates such as petroleum naphthas, etc. Usually it ispreferred to apply the compounds in the form of aqueous emulsions. Thesecan be prepared by customary techniques-agitation of the glycidolderivative with water and a conventional emulsifying agent such as analkylphenoxypoly-(ethyleneoxy)ethanol, polyoxyethylene sorbitanmonopalmitate, polyoxyethylene lauryl ether, polyoxyethylenepolyoxypropylene stearate, sorbitan monopalmitate, sorbitan monolaurate,and the like. The concentration of the glycidol derivative in thedispersion this last term being herein employed in a generic sense toinclude solutions and emulsionsis not critical and may 'be varieddepending on such circumstances as the solubility characteristics of thederivative, the amount thereof to be deposited on the fibers, theviscosity of the dispersion, etc. In general, a practical range ofconcentration would be from about 1% to about 25%.

The dispersion of the glycidol derivative will also contain a catalyst,whereby to promote curing (in a subsequent step) of the glycidolderivative to form an insoluble product in situ on the textile fibers.As the curing catalyst we prefer to use an acid or an acid-acting agent,that is, a substance not usually classified as an acid but which acts assuch. Typical examples of curing catalysts are citric acid, acetic acid,acetic acid anhydride, butyric acid, caproic acid, phthalic acid,phthalic acid anhydride, tartaric acid, aconitic acid, oxalic acid,succinic acid, succinic acid anhydride, lactic acid, maleic acid, maleicacid anhydride, fumaric acid, glutaconic acid, malonic acid, acetoaceticacid, naphthalic acid, trimellitic acid, phosphoric acid, sulfuric acid,boric acid, perchloric acid, persulfuric acid, and p-toluenesulfonicacid; metal salts, such as zinc fluoroborate, magnesium perchlorate,copper fiuoroborate, zinc sulfate, zinc persulfa-te, zinc phosphate,ferrous perchlorate, nickel fluoroborate, manganese phosphate andstrontium fluoroborate. Boron trifiuoride is also a useful agent for thepurpose, and is particularly preferred in the form of its adduct withpiperidine, this adduct being soluble in organic solvents. In additionto the above-named substances, one can use any of the acid oracid-acting agents known in the art to promote the insolubilization ofepoxides. The curing catalyst is generally employed in a proportion ofabout 1 to 20%, based on the weight of glycidol derivative in thedispersion.

The dispersions containing the ingredients described above may bedistributed on the textile material by any of the usual methods, forexample, by spraying, brushing, padding, dipping, etc. A preferredtechnique involves immersing the textile in the dispersion and thenpassing it through squeeze rolls to remove the excess of liquid. Suchtechniques as blowing air through the treated textile may be employed toreduce the amount of liquid which exists in interstices between fibrouselements. In any case, the conditions of application are so adjustedthat the textile material contains the proportion of glycidol derivativedesired. Generally, this amount is about from 0.5 to 20%, based on theweight of the textile material but it is obvious that higher proportionsmay be used for special purposes. In treating textiles such as fabricsthe amount of glycidol derivative is usually limited to a range of about0.5 to 10% to attain the desired end such as shrink resistance withoutinterference with the hand of the textile.

After application of the glycidol derivative, the treated textile iscured (heated) to effect an insolubilization of the applied compound andto promote bonding thereof to the textile. Although the mechanism ofbonding has not been identified, it is believed to involve chemicalcombination between the epoxy group of the glycidol moiety with activeradicals in the textile substrate, these active radicals includingcarboxyl, hydroxyl, amino, and thiol groups. Such groups are, of course,present in many textile materials including wool, animal hair, leather,and other proteinaceous materials; cotton, rayon, linen, and othercellulosic fibers; nylon, polyurethanes, and many other syntheticfibers.

In cases where the glycidol derivative is applied as a dispersion, thatis, a solution, emulsion, or suspension, the solvent or other volatiledispersing medium is preferably evaporated prior to the curingoperation. Such prior evaporation is not a critical step and theevaporation may be simply effected as part of the curing step. Thetemperature applied in the curing step is not critical and usually iswithin the range from about 50 C. to about 150 C. It is obvious that thetime required for the curing will vary with such factors as thereactivity of the selected glycidol derivative, the type of textilematerial, and particularly the temperature so that a lower curingtemperature will require a longer curing time and vice versa. It will befurther obvious to those skilled in the art that in any particular casethe temperature of curing should not be so high as to cause degradationof the textile or the glycidol derivative. In many cases an adequatecure is effected by heating the treated textile in an oven at about C.for about 5 to 60 minutes.

Although the present invention is of particular advantage in itsapplication to wool, this is by no means the only type of fiber whichcomes into the ambit of the invention. Generically, the invention isapplicable to the treatment of any textile material and this materialmay be in any physical form, e.g., bulk fibers, filaments, yarns,threads, slivers, roving, top, Webbing, cord, tapes, woven or knittedfabrics, felts or other non-woven fabrics, gar ments or garment parts.Illustrative examples of textile materials to which the invention may beapplied are: Polysaccharide-containing textiles, for instance, thoseformed of or containing cellulose or regenerated celluloses, e.g.,cotton, linen, hemp, jute, ramie, sisal, cellulose acetate rayons,cellulose acetate-butyrate rayons, saponified acetate rayons, viscoserayons, cuprammonium rayons, ethyl cellulose, fibers prepared fromamylose, algins, or pectins; mixtures of two or more of suchpolysaccharide-containing textiles. Protein-containing textiles, forinstance, those formed of or containing Wool, silk, animal hair, mohair,leather, fur, regenerated protein fibers such as those prepared fromcasein, soybeans, peanut protein, zem, gluten, egg albumin, collagen, orkeratins, such as feathers, animal hoof or horn. Mixtures of any two ormore protein-containing textiles. Mixtures of polysaccharide-containingtextiles and protein-containing textiles, e.g., blends of wool andcotton; wool and viscose, etc. Textiles formed of or containingsynthetic resins, e.g., alkyd resins, polyvinyl alcohol, partiallyesterified or partially etherfied polyvinyl alcohol, nylon,polyurethanes, polyethylene glycol terephthalate, polyacrylonitrile,poly ethylene, polypropylene, polyvinyl chloride, and polyvinylidenechloride. Blends of natural fibers such as cotton or Wool with syntheticfibers such as nylon, polyethyleneglycol terephthalate, acrylonitrile,etc. Inorganic fibers such as asbestos and glass fibers. Theapplications of the teachings of the invention may be for the purposesof obtaining functional or decorative efiects such as shrinkproofing,developing permanent crease qualities, sizing, finishing, increasingabrasion resistance, increasing gloss or transparency, increasingwater-, oil-, and soil-repellency, increasing adhesion or bondingcharacteristics of the substrates with rubber, polyester resins, etc.

EXAMPLES The invention is further demonstrated by the followingillustrative examples.

Washing procedure for shrinkage tests: The samples were washed in areversing agitator-type household washing machine, using a three-poundload, a water temperature of 105 F., and a low-sudsing detergent in aconcentration of 0.1% in the wash liquor. The wash cycle itself was for75 minutes, followed by the usual rinses and spin-drying. The dampmaterial from the washer was then tumble-dried in a household-typeclothes dryer. The dried samples were measured to determine their lengthand Width and the shrinkage calculated from the original dimensions.

Example 1.-Preparation of Polymer A V The starting material for thissynthesis was a commercial liquid polyurethane derived from apolyalkyleneether triol, having a molecular weight of about 3000 and anisocyanate (-NCO) content of 4%. It is believed to have the structure OtL-NH NCO Example 2.--Preparation of Polymer B The starting material forthis synthesis was a commercial liquid polyurethane having a molecularweight of about 2000 and an isocyanate content of 6.5%. It is believedto have the structurewherein A represents the residue of apolytetramethyleneether glycol containing about thirteen Thepolyurethane (200 g., providing approximately 0.31 mole of NCO) wasdissolved in 300 g. of toluene. To this solution there was added 23 g.(0.31 mole) of glycidol, followed by 5 drops of dibutyltin laurate and100 mg. of triethylene diamine. The solution was heated at 65 C.overnight. At the end of that time, examination of the solution byinfrared analysis revealed that all of the available-NCO had reactedwith the hydroxy group of the glycidol.

Example 3.Preparation of Polymer C The starting material for thissynthesis was a polypropylene-ether glycol of molecular weight about6000, and having the structurewherein n is about 100.

The glycol was reacted with toluene diisocyanate in conventional mannerto produce an isocyanate-terminated polyurethane CH: O

OCN NCO wherein n is about 100. I

The polyurethane intermediate was then reacted with glycidol in the samemanner as described in Example 2 to yield the glycidol-modifiedpolyurethane of the structure wherein n is about 100.

Example 4.Preparation of Polymer D Example 5.Preparation of PolymerEmulsion This example illustrates the preparation of emulsions of theglycidol-modified polyurethanes.

To a 100-gram sample of a solution containing 40 g. of glycidol-modifiedpolyurethane and 60 g. of toluene, there was added 2 g. of a commercialoil-soluble emulsifying agentan alkylphenoxy poly(ethyleneoxy)ethanol.The mixture was stirred rapidly and 50 ml. of water were slowly added.The thick water-in-oil emulsion was transferred to a blender and, whilestirring at high speed, there was added 200 ml. of water containing 2 g.of a watersoluble emulsifier-an alkylphenoxy poly(ethyleneoxy)- ethanol.The resulting oil-in-water emulsion of the glycidol-modifiedpolyurethane was used as a stock supply and diluted with water asnecessary.

Example 6.Application of Glycidol-Modified Polyurethanes to Fabrics Abrown-dyed worsted, 100% wool fabric was employed to test theeffectiveness of various glycidol-modified poly- 'urethanes. Thesepolymers were applied either as solutions in an organic solvent or asaqueous emulsions. A catalyst (as indicated below) was added to thepolymer solutions or emulsions. Samples of the fabric were wet-out withthe polymer solution or emulsion, run through squeeze rolls to removeexcess liquid and leave a wet pick-up of 50- The fabrics were air-dried,then cured in an oven at 300 F. for 20 minutes. The treated fabrics werethen washed in the manner detailed above and the shrinkage determined.

The materials used and the results obtained are summarized in thefollowing table.

Add-on of Area polymer, shrinkage percent after two Catalyst and amountbased on 75-min thereof, percent based weight of washes, Solvent onweight of polymer fabric percent Pol er:

A 0113-0013.... BFv iperidlne-. 20 3 1 A..- CHrCHzOH d 20 1 2, A. Aq.emulsion- Mg fiuoborate.-- 20 3 0 A. ....do Zn fluoborate..- 1 2,0 13.....do Mg fluoborate... 20 2 2 C..- CHs-C 01s.... BFa-piperidineu l5 33, 0 D CHs-CC1s .-do 20 1 2,0 None (control) 32 Example 7 scribedheremabove. The condmons of apphcation may An aqueous emulsion wasprepared containing 3% of Polymer A and 0.6% of magnesium fluoroborate.

The emulsion was padded onto samples of worsted, 100% wool fabric whichwere then squeezed through rolls to a wet pick-up of 70%. Afterair-drying at room temperature, the fabrics were stored at 22 C. for onemonth.

At the end of this time, one sample of the treated fabric was at 310 F.for 20 minutes, then subjected to two 75-minute washes as abovedescribed. The area shrinkage was found to be 2% Another sample of thetreated fabric, without any curing step, was subjected to the washingtest. It was found that this uncured sample shrank 25% in area. Thisindicated that the applied polymer had remained inactive during thestorage period.

Permanent Press A particular embodiment of this invention is concernedwith the production of wool products which exhibit not only shrinkresistance but also permanent press qualities. Heretofore, it has beendifficult to impart this combination of useful properties to wool.Existing wool shrinkproofing treatments do lead to dimensionally-stablefabrics; however, when the fabrics are washed or dry-cleaned they have amussy appearance and must be pressed. Creases have been set in woolengarments by, for example, treatment with reducing agents such asammonium thioglycollate or sodium bisulphite. The creases, however, donot withstand aqueous laundering nor generally more than 1 or 2dry-cleanings. Of course, no shrinkproofing is attained with thesecreasing procedures. Attempts to combine wool shrinkage treatments withcreasing treatments have not been successful in that although shrinkagecan be controlled, creases are lost after aqueous laundering and thefabrics need ironing for neat appearance. Various materials such asmelamine-formaldehyde resins, ureaformaldehyde resins,dihydroxy-ethylene dimethylol urea, or alkyl carbamates, which arecommercially used in producing permanently creased garments of cotton orcottonsynthetic blends have proved entirely unsuccessful when applied towool.

However, these problems are obviated by the present invention. Byapplication of our glycidol derivatives to wool fabrics one attainsresistance to shrinkage, a smooth wrinkle-free appearance after washingor dry-cleaning so that no ironing is required, and creases and pleatsimparted to the fabric are permanentthey withstand repeated aqueouslaundering or non-aqueous dry-cleaning.

This embodiment of the invention is most profitably practiced in asystem which incorporates a delayed cure, that is, the glycidolderivative is applied to the fabric but curing is delayed until thefabric has been made up into the desired product which may be, forexample, a completed garment. The curing then not only bonds theglycidol derivative to the fabric, but also renders permanent thecreases or pleats which have been imparted to the fabric. Typical waysof practicing this embodiment of the invention are described in detailbelow:

The glycidol derivative is applied to the fabric, preferaby using anemulsion of the glycidol derivative, as debe adjusted to vary the amountof glycidol derivative deposited on the fabric. Usually, it is preferredto deposit about 0.2 to 20%, based on the weight of the fabric. In apreferred modification of the invention, N-methylol acrylamide(hereinafter referred to as NMA) and an aldehydebisulphite isincorporated in the emulsion. However, as hereinafter explained, the NMAand aldehyde-bisulphite may be added at a later stage in the process.The treated fabric is then dried to remove the water in which theglycidol derivative and other agents were dispersed for the applicationstep. The drying may be in air at ordinary (room) temperature, or, warmair may be applied to increase the rate of evaporation. To avoidpremature curing, the temperature of the treated fabric should be keptbelow about 50 C. However, since curing does not occur immediately,short exposures to higher temperatures are permissible.

The fabric containing the glycidol derivative in its uncured state isthen made up into the desired product. This may be, for example, agarment, in which case the fabric would be subjected to the usualgarment-making operations of cutting, sewing, and pressing. Included inthese operations would be formation of creases or pleats in selectedareas by the usual pressing methods employed by the tailor. In the eventthat the NMA and aldehyde-bisulphite were not co-applied with theglycidol derivative, these agents may be applied to the textile duringthe moistening step which commonly forms a part of the pressingoperation. For example, an aqueous solution of NMA andaldehyde-bisulphite may be sprayed onto the textile, particularly inthose areas where it is intended to form creases or pleats. Enough ofthe solution is usually applied to furnish the following amounts (basedon the weight of fabric): N=MA-about 2 to 20%, preferably about 2 to10%; aldehyde-bisulphite-abOut 0.5 to 10%, preferably about 2 to 4%. Itis to be particularly emphasized that production of garments need notfollow directly after application of the glycidol derivative to thefabric. Indeed, the fabric containing the uncured glycidol derivativecan be held for long periods without danger of spontaneous curing. Theglycidol derivatives of the invention are particularly characterized bytheir stability, i.e., their ability to remain in an uncured state forlong periods of time. Moreover, their stability is not affected bymoisture. If moisture is applied (as necessary in certain garmentfabricating steps) there is no danger of premature curing.

The garment or other textile article is then subjected to a curingoperation to insolubilize the glycidol derivative and bond it to thewool fibers. Typically, the curing is accomplished by placing thegarments in an oven where they are maintained at a temperature and for atime sufficient to cause the desired curing effect. In general,temperatures of at least 50 C., preferably about C., are applied for aperiod of about 5-60 minutes. The product after removal from the oven isnow ready for use or for sale and, as previously noted, exhibits notonly resistance to shrinkage when washed but also retains its pleats,creases, or other conformations imparted to the garment. Also, whenwashed, the products retain a neat appearance free from wrinkling ormussiness so 13 that they are truly press-free, i.e., no pressing isneeded even after repeated washings.

The aldehyde-bisulphites used in accordance with the invention are knownsubstances prepared by reacting an aldehyde with an alkali metalbisulphite, usually sodium bisulphite. Many difierent aldehydes may beused (in the form of their bisulphites), as for example: saturatedaliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde,butylaldehyde, isobutylaldehyde, valeraldehyde, isovaleraldehyde,caproaldehyde, enanthaldehyde, caprylaldehyde, pelargonaldehyde,capraldehyde, lauraldehyde, palmitic aldehyde, stearaldehyde, and thelike; unsaturated aliphatic aldehydes, such as acrolein, crotonaldehyde,tiglic aldehyde, citronellal, citral, and the like; alicyclicmonofunctional aldehydes, such as formylcyclohexane, and the like;aliphatic dialdehydes, such as glyoxal, pyruvaldehyde, malonaldehyde,succinaldehyde, glutaraldehyde, adipaldehyde, maldealdehyde, and thelike; substituted aldehydes, such as chloral, aldol, and the like;aromatic aldehydes wherein the aldehyde group is attached to a ring,such as benzaldehyde, phenylacetaldehyde, p-tolualdehyde,p-isopropylbenzaldehyde, o-chlorobenzaldehyde, o-nitrobenzaldehyde,m-nitrobenzaldehyde, p-nitrobenzaldehyde, salicylaldehyde, anisaldehyde,vanillin, veratraldehyde, piperolnal, a-naphthaldehyde, anthraldehyde,and the like; and aromatic aldehydes wherein the aldehyde group is notattached to a ring, such as phenylacetaldehyde, cinnamaldehyde, and thelike; and heterocyclic aldehyde, such as a-formylthiophene,a-formylfurfural, fur-fural, tetrahydrofurfural, and the like. Ingeneral, we prefer to use glyoxal bisulphite.

Below are listed, by way of example, alternative techniques forpracticing this embodiment of the invention.

Technique A:

1. Apply glycidol derivative to fabric.

2. Dry treated fabric and make up garment therefrom.

3. Spray garment with aqueous solution of NMA and aldehyde-bisulphite,for example, to an approximately 4050% wet pick-up, using an aqueoussolution containing about to of NMA and about 1 to 3% ofaldehyde-bisulphite.

4. Steam-press garment to desired configuration.

5. Oven cure garment.

Technique B (preferred):

1. Apply to fabric an aqueous emulsion containing the glycidolderivative, NMA, and aldehyde-bisulphite. Typically, this emulsion willcontain about 1 to 4% of the glycidol derivative, about 5 to 10% of NMA,and about 1 to 3% of aldehyde-bisulphite. To inhibit prematurepolymerization, it is preferred to add to the emulsion about 5 to 10% ofa water-soluble alcohol such as methanol, ethanol, isopropanol, or thelike.

2. Dry treated fabric and make up garment therefrom.

3. Spray garment with water, for example, to about 40-50% wet pick-up.

4. Steam-press garment to desired configuration.

5. Oven cure garment.

Technique B (preferred):

1. Apply to fabric an aqueous emulsion containing the glycidolderivative and NMA. Typically, this emulsion will contain about 1 to 4%of the glycidol derivative and about 5 to 10% NMA.

2. Dry treated fabric and make up garment therefrom.

3. Spray garment with water containing about 1 to 4%aldehyde-bisulphite, to about 4050% wet pickup.

4. Steam-press garment to desired configuration.

5. Oven cure garment.

Technique C:

1. Prepare garment from fabric.

2. Apply to garment an aqueous emulsion containing theglycidol-derivative, NMA, and aldehyde-bisulphite.

3. Steam press garment while still tion of the emulsion.' 4. Oven curegarment.

damp from applica- This embodiment of the invention is furtherdemonstrated by the following illustrative example.

Example I 8 An aqueous emulsion of 3.5% Polymer A was prepared asdescribed in Example 5. This stock emulsion was then used to prepare aseries of emulsions containing different aldehyde-bisulphites (asindicated in the following table) plus other ingredients, the same ineach. Thus, each emulsion contained 3.5% of Polymer A (described inExample 1), 0.7% of zinc fluoroborate, 8% NMA,-2% aldehyde-bisulphite,and 10% (by volume) of ethanol.

A piece of worsted 100% wool slack fabric was cut into samples whichwere treated with the emulsions, using the following procedure in eachcase. The emulsion was padded onto the fabric which was then squeezedthrough rolls to a wet pick-up of 50%. While still damp, the

fabrics were creased, usinga tailorls hot-head press. The creasedsamples were then cured in an oven at 310 F; for.20 minutes. 1 i r Thecured samples were then subjected to a series of washes (as describedabove) and tumble-dried after each wash. The samples were evaluated forsmoothness and crease retention after one or more cycles of washing andtumble-drying.

Smoothness and crease retention were determined in accordance with AATCCMethods 88A-II-C and 88C- II-C, respectively. In these tests theevaluation is done by comparison with photographic standards and ratingsare given from 1 to 5 with a rating of 1 being very poor and 5 beingexcellent.

The results obtained are tabulated below.

No. of wash-dry cycles Crease retention Smooth- Gluaraldehydebisulphiteo Do Pro gonaldehyde-bisulphite.

Having thus described our invention, we claim:

1. A process of treating proteinaceous textile material to improve itsproperties, which comprises (a) depositing on the textile material anaqueous emulsion containing about 5 to 10% of N-niethylbl acrylamide,about 1 to 3% of an aldehyde-bisulphite, and about 1 to 4% of aglycidol-modified polyurethane of the structure wherein:

A is the residue of a polyether polyol or polyester polyol having avalence of n,

R is a hydrocarbon radical containing at least two carbon atoms, a

R is hydrogen, halogen, lower alkoxy, or a radical of the structure n isan integer from 2 to 4, and x is an integer from 1 to 2, (b) and curingthe so-treated textile material by heating it at about 50 to 150 C. 2.The process of claim 1 wherein A is the residue of a polyalkyleneetherglycol and n is 2.

3. The process of claim 1 wherein A is the residue of apolyalkyleneether triol and n is 3.

4. The process of claim 1 wherein the sole constituents of A are carbon,hydrogen, and oxygen. 5. The process of claim 1 wherein is the tolyleneradical.

6. The process of claim 1 wherein the textile material is wool.

7. The process of claim 1 wherein the treated textile material from Step(a) is subjected to garment-fabricating operations including cutting,sewing, and pressing, prior to curing the textile according to Step (b).

References Cited UNITED STATES PATENTS 3,684,429 8/1972 Tesoro et al.8--127.6 3,542,505 11/1970 Pittman et al. 8127.6 3,523,750 8/ 1970Tesoro 8127.6 3,519,383 7/1970 Peters 8-127.6 3,652,212 3/1972 Machell8-128 X 2,730,427 1/ 1956 Suen -8128 X 3,677,693 7/1972 Robinson et al8-128 X OTHER REFERENCES Marsh: Crease Resisting Fabrics, pub. 1962 byReinhold Publishing Corp., New York, pages 94-99.

HERBERT B. GUYNN, Primary Examiner US. Cl. X.R.

8-115.5, 128 A, 184, 196; 117-138.8 A, 138.8 N, 139.4, 141; 260- 775 AP

